EP0728724A1 - Diethers suitable for use in the preparation of Ziegler-Natta catalysts - Google Patents

Diethers suitable for use in the preparation of Ziegler-Natta catalysts Download PDF

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EP0728724A1
EP0728724A1 EP96102586A EP96102586A EP0728724A1 EP 0728724 A1 EP0728724 A1 EP 0728724A1 EP 96102586 A EP96102586 A EP 96102586A EP 96102586 A EP96102586 A EP 96102586A EP 0728724 A1 EP0728724 A1 EP 0728724A1
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bis
methoxymethyl
radicals
equal
iii
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Giampiero Morini
Antonio Cristofori
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Basell Poliolefine Italia SRL
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Montell North America Inc
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/162—Unsaturated ethers containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/164—Unsaturated ethers containing six-membered aromatic rings
    • C07C43/168—Unsaturated ethers containing six-membered aromatic rings containing six-membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
    • C07C43/1747—Unsaturated ethers containing halogen containing six-membered aromatic rings containing six membered aromatic rings and other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/24—Anthracenes; Hydrogenated anthracenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
    • C07C2603/28—Phenalenes; Hydrogenated phenalenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

Definitions

  • the present invention concerns a new class of diethers and a new process for their synthesis.
  • DMSO dimethyl sulfoxide
  • paraformaldehyde rendered anhydrous at ambient temperature and at a pressure of 2 torr for 8 hours
  • sodium ethylate dissolved in 6 mL of ethanol.
  • microspheroidal MgCl 2 ⁇ 2.1 C 2 H 5 OH is prepared as follows.
  • the alcohol is removed from the product thus obtained at temperatures that are gradually increased from 50°C to 100°C in nitrogen atmosphere until the alcohol content is reduced to 2.1 moles per mole of MgCl 2 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Diethers suitable for use in the preparation of Ziegler-Natta catalysts having the formula:
Figure imga0001
 where A, B, C, and D are carbon atoms or heteroatoms, v, x, and y are 0 or 1; u and z are either 0, 1, or 2; the radicals R and RI, equal or different, are H; halogens; linear or branched alkyl radicals; cycloalkyl, aryl, alkylaryl, and aralkyl radicals; the RII radicals, equal or different, are linear or branched alkyl radicals; cycloalkyl, aryl, alkylaryl, and aralkyl radicals; at least two R radicals can be bonded to one another to form saturated or unsaturated condensed cyclic structures, optionally substituted with RIII radical selected from halogens; linear or branched alkyl radicals; cycloalkyl, aryl, alkylaryl, and aralkyl radicals; said radicals from R to RIII optionally containing at least one heteroatom.

Description

  • The present invention concerns a new class of diethers and a new process for their synthesis.
  • The diethers of the present invention are particularly suited for the preparation of Ziegler-Natta catalysts to which they confer qualities far superior, in terms of balanced activity and stereospecificity in the (co)polymerization of olefins, to those that are obtained with the ethers known in the art. By olefins one refers in particular to the CH2=CHR compounds where R is hydrogen, or a C1-C6 alkyl or aryl radical.
  • The diethers of the present invention have the following general formula (I)
    Figure imgb0001
     where A, B, C, and D are carbon atoms or heteroatoms selected from the group consisting of N, O, Si and S; v, x, and y are 0 or 1; u and z are either 0, 1, or 2;
    provided that when u = 0:
    • i) A, B, and C are carbon atoms and v, x, and y are equal to 1; or
    • ii) A is a nitrogen atom, B and C are carbon atoms, v is equal to 0, and x and y are equal to 1; or
    • iii) A and B are nitrogen atoms, C is a carbon atom, v and x are equal to 0, and y is equal to 1; or
    • iv) A and B are carbon atoms, C is a nitrogen atom, v and x are equal to 1, and y is equal to 0;
    when u = 1:
    • 1) A, B, C, and D are carbon atoms, v, x, and y are equal to 1, and z is equal to 2; or
    • 2) A and B are carbon atoms, C is a nitrogen atom, D is an oxygen atom, v and x are equal to 1, y and z are equal to 0; or
    • 3) A, B, and C are carbon atoms, D is an oxygen, nitrogen, sulfur, or silicon atom, v, x, and y are equal to 1, and z is equal to 0 when D is an oxygen or sulfur atom, equal to 1 when D is a nitrogen atom, and equal to 2 when D is a silicon atom;
    when u = 2:
       A, B, and C are carbon atoms, D represents two carbon atoms bonded to each other by a single or double bond, v, x, and y are equal to 1, and z is 1 when the pair of carbon atoms D is bonded by a double bond, and z is 2 when said pair is bonded by a single bond;
    radicals R and RI, equal or different, are hydrogen; halogens, preferably Cl and F; C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 aralkyl radicals; the RII radicals, equal or different, are C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 aralkyl radicals, and two or more of the R radicals can be bonded to each other to form condensed cyclic structures, saturated or unsaturated, optionally substituted with RIII radicals wherein RIII is a halogen, preferably Cl and F; C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7- C20 aralkyl radicals; said radicals from R to RIII optionally containing one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both.
  • The heteroatoms optionally present in the radicals from R to RIII are preferably selected from the group consisting of N, O, S, P, Si, and halogens, in particular Cl and F.
  • A preferred group of the compounds of general formula (I) consists of the compounds of general formula:
    Figure imgb0002
     where the radicals from R to RII are as defined above for formula (I).
  • In particular, two or more of the R radicals can be bonded to each other to form one or more condensed cyclic structures, preferably benzenic, optionally substituted by RIII radicals having the meaning specified above for formula (I).
  • Specially preferred are the compounds of formula:
    Figure imgb0003
     where the R radicals, equal or different, are hydrogen; halogens, preferably Cl and F; C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 aralkyl radicals, optionally containing one or more heteroatoms selected from the group consisting of N, O, S, P, Si and halogens, in particular Cl and F, as substitutes for carbon or hydrogen atoms, or both; the radicals RI and RII are as defined above for formula (I).
  • Specific examples of compounds comprised in formula (II) are:
    1,1-bis(methoxymethyl)-cyclopentadiene;
    1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene;
    1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene;
    1,1-bis(methoxymethyl)-2,3,4,5-tetrafluorocyclopentadiene;
    1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene;
    1,1-bis(methoxymethyl)indene;
    1,1-bis(methoxymethyl)-2,3-dimethylindene;
    1,1-bis(methoxymethyl)-4,5,6,7-tetrahydroindene;
    1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene;
    1,1-bis(methoxymethyl)-4,7-dimethylindene;
    1,1-bis(methoxymethyl)-3,6-dimethylindene;
    1,1-bis(methoxymethyl)-4-phenylindene;
    1,1-bis(methoxymethyl)-4-phenyl-2-methylindene;
    1,1-bis(methoxymethyl)-4-cyclohexylindene;
    1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene;
    1,1-bis(methoxymethyl)-7-trimethylsilylindene;
    1,1-bis(methoxymethyl)-7-trifluoromethylindene;
    1,1-bis(methoxymethyl)-4,7-dimethyl-4,5,6,7-tetrahydroindene;
    1,1-bis(methoxymethyl)-7-methylindene;
    1,1-bis(methoxymethyl)-7-cyclopenthylindene;
    1,1-bis(methoxymethyl)-7-isopropylindene;
    1,1-bis(methoxymethyl)-7-cyclohexylindene;
    1,1-bis(methoxymethyl)-7-tert-butylindene;
    1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene;
    1,1-bis(methoxymethyl)-7-phenylindene;
    1,1-bis(methoxymethyl)-2-phenylindene;
    1,1-bis(methoxymethyl)-1H-benz[e]indene;
    1,1-bis(methoxymethyl)-1H-2-methylbenz[e]indene;
    9,9-bis(methoxymethyl)fluorene;
    9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene;
    9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene;
    9,9-bis(methoxymethyl)-2,3-benzofluorene;
    9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene;
    9,9-bis(methoxymethyl)-2,7-diisopropylfluorene;
    9,9-bis(methoxymethyl)-1,8-dichlorofluorene;
    9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene;
    9,9-bis(methoxymethyl)-1,8-difluorofluorene;
    9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene;
    9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene;
    9,9-bis(methoxymethyl)-4-tert-butylfluorene;
    1,1-bis(1'-butoxyethyl)-cyclopentadiene;
    1,1-bis(1'-isopropoxy-propyl)cyclopentadiene;
    1-methoxymethyl-1-(1'-methoxyethyl)-2,3,4,5-tetramethylcyclopentadiene;
    1,1-bis(α-methoxybenzyl)indene;
    1,1-bis(phenoxymethyl)indene;
    1,1-bis(1'-methoxyethyl)-5,6-dichloroindene;
    1,1-bis(phenoxymethyl)-3,6-dicyclohexylindene;
    1-methoxymethyl-1-(1'-methoxyethyl)-7-tert-butylindene;
    1,1-bis[2-(2'methoxypropyl)]-2-methylindene;
    3,3-bis(methoxymethyl)-3H-2-methylbenz[e]indene;
    9,9-bis(α-methoxybenzyl)fluorene;
    9,9-bis(1'-isopropoxy-butyl)-4,5-diphenylfluorene;
    9,9-bis(1'-methoxyethyl)fluorene;
    9-(methoxymethyl)-9-(1-methoxyethyl)-2,3,6,7-tetrafluorofluorene;
    9-methoxymethyl-9-pentoxymethylfluorene;
    9-methoxymethyl-9-ethoxymethylfluorene;
    9-methoxymethyl-9-(1'-methoxyethyl)-fluorene;
    9-methoxymethyl-9-[2-(2-methoxypropyl)]-fluorene;
    5,5-bis(methoxymethyl)-1,5-pyrindine; and
    5,5-bis(methoxymethyl)-6,7-dimethyl-1,5-pyrindine.
  • Other examples of 1,3-diethers comprised in formula (I) are:
    1,1-bis(methoxymethyl)-2,5-cyclohexadiene;
    1,1-bis(methoxymethyl)-benzonaphthene;
    4,4-bis(methoxymethyl)-4H-cyclopenta[d,e,f]phenanthrene;
    9,9-bis(methoxymethyl)-9-10-dihydroanthracene;
    7,7-bis(methoxymethyl)-7H-benz[d,e]anthracene;
    4,4-bis(methoxymethyl)-1-phenyl-1,4-dihydronaphthalene
    5,5-bis(methoxymethyl)-1,3,6-cycloheptatriene;
    5,5-bis(methoxymethyl)-10,11-dihydro-5H-dibenzo[a,d] cycloheptene;
    5,5-bis(methoxymethyl)-5H-dibenzo[a,d]cycloheptene;
    9,9-bis(methoxymethyl)xanthene;
    9,9-bis(methoxymethyl)-2,3,6,7-tetramethylxanthene;
    9,9-bis(methoxyisobutyl)thioxanthene;
    4,4-bis(methoxymethyl)-1,4-pyran;
    9,9-bis(methoxymethyl)-N-tert-butyl-9,10-dihydroacridine;
    4,4-bis(methoxymethyl)-1,4-chromene;
    4,4-bis(methoxymethyl)-1,2,4-oxazine;
    1,1-bis-(methoxymethyl)benzo-2,3,1-oxazine;
    2.2-bis(methoxymethyl)-3,4,5-trifluoroisopyrrole; and
    4,4-bis(1'-methoxyethyl)benzo-N-phenyl-1,4-dihydropyridene.
  • The diethers of the present invention can be synthesized by various reactions. One of them consists of causing to react, in the presence of a base, a compound of the following general formula:
    Figure imgb0004
     where u, v, x, y, z, A, B, C, D, and the R radicals are as defined for general formula (I), with compounds of the formula XC(RI)2-ORII, where X represents Cl, Br, and I, and RI and RII are as defined for general formula (I). However, this way of synthesizing has the inconvenience of producing low yields.
  • The diethers of the present invention can also be synthesized from the corresponding diols by an etherification reaction as described, for example, in European patent applications EP-A-361493 and EP-A-487035, both filed on behalf of the Himont Inc. The etherification reaction described in these applications requires that a diol, or the corresponding alkaline alcoholate, in a suitable organic solvent is reacted with an RIIX compound, or a (RII)2SO4 compound, where RII is as defined for general formula (I), and X is Cl, Br, I, CH3SO3, C6H5-SO3, or p-CH3-C6H4-SO3, in the presence of a base. According to the examples of said applications the etherification reaction is carried out by mixing the diol, or corresponding alkaline alcoholate, with the base in an organic solvent, and then adding the RIIX or (RII)2SO4 compound. Optionally base and RIIX or (RII)2SO4 compound can added subsequently.
  • This reaction produces yields that do not exceed 80%, and in same cases requires long synthesis periods.
  • Now has been found a synthesis process that allows one to obtain the diethers of the present invention with higher etherification yields. Also, less reaction time is needed for the etherification reaction. Said process can be used for the synthesis of the propane-1,3-diethers described in the above mentioned European patent application EP-A-361493.
  • Another object of the present invention is the process for the synthesis of diethers of general formula (III)
    Figure imgb0005
     where the R7 and R8 radicals, equal or different, are hydrogen or C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 aralkyl radicals; the R4, R5, R9, and R10 radicals, equal or different, have the same meaning as defined for the R7 and R8 radicals; the R6 and R11 radicals have the same meaning as the R7 and R8 radicals except for the hydrogen; moreover, two or more radicals from R4 to R10 can be bonded to form a cyclic structure; said radicals from R4 to R11 optionally containing one or more heteroatoms, as substitutes for one or more carbon or hydrogen atoms, or both, selected from N, O, S, P, Si and halogens, preferably Cl and F.
  • Said process comprises the following steps:
    • a) mixing a diol of general formula (IV)
      Figure imgb0006
       where the radicals from R4 to R10 are as defined for general formula (III), with a compound or mixture of compounds selected from the compounds of general formulae R6X (V), or general formula R11X (VI), where X is Cl, Br, I, CH3SO3, C6H5-SO3, or p-CH3-C6H4-SO3, or of general formula (R6)2SOn (VII), or of general formula (R11)2SOn (VIII), where R6 and R11 have the meaning as defined for general formula (III), and n is 3 or 4, in a solvent which is basically nonreactive toward the reagents; and then
    • b) adding a base which is substantially inert towards the compounds of general formulae (V) to (VIII), and is capable of forming the alcoholated derivative of the corresponding diol (IV) under the reaction conditions.
  • Preferably, the above mentioned bases are selected from the bases of alkaline metals. Examples of bases that can be used in the process of the present invention are sodium hydride and sodium hydroxide. In the specific case where sodium hydroxide is used, the preferred solvent is the dimethyl sulfoxide.
  • Preferably the base is added gradually. For example one can introduce the base in a period of time ranging from 10 minutes to 4 hours.
  • Examples of solvents suitable for use in the process of the present invention include tetrahydrofuran, dimethyl sulfoxide, diethyl ether, aliphatic hydrocarbons, such as pentane, heptane, hexane, or aromatic hydrocarbons such as toluene and benzene, and dimethylformamide.
  • Specific reaction conditions, such as temperature and pressure, are not crucial for the reaction to occur; for example the temperature can range from 0° to 100°C, and the operation can take place at ambient pressure.
  • It is preferable to carry out the above mentioned reaction by using quantities of the compound or mixture of compounds of formulae (V) to (VIII) in excess with respect to the diol (IV). In particular, the molar ratio of the diol to the compound or mixture of compounds (V)-(VIII) is preferably comprised from 1:3 to 1:15.
  • Examples of synthesis of diols of formula (IV) are already known in literature; for example synthesis processes are disclosed in above cited European patent applications EP-A-361493 and EP-A-487035, both filed on behalf of Himont Inc.
  • The diols corresponding to the diethers of formula (I) can be prepared according to various known synthesis processes, for example, by aldol condensation of the corresponding unsaturated cyclic compounds, such as fluorene, indene, cyclopentadiene, with proper aldehydes (see Acta Chemica Scandinavica 21, 1967, pp. 718-720, for example).
  • Examples of specific diols corresponding to the diethers of formula (I) and their related synthesis disclosed in literature, are 9,9-bis(hydroxymethyl)fluorene (see Acta Chemica Scandinavica 21, 1967, pp. 718-720), 9-hydroxymethyl-9-(α-nethyl)hydroxymethylfluorene (see Chemical Abstract, CAS number: 101168-93-8), 9-(α-methyl)hydroxymethyl-9-(α'-methyl)hydroxymethylfluorene (see Beilstein, registration number: 101594-61-0), and 9-(α-phenyl)hydroxymethyl-9-(α'-phenyl)hydroxymethylfluorene (see Beilstein, registration number: 103210-68-0).
  • The following examples are given in order to illustrate and not limit the present invention.
    • Synthesis of 9,9-bis(hydroxymethyl)fluorene
  • Into a 500 mL flask, in anhydrous atmosphere, are introduced in order: 100 mL of dimethyl sulfoxide (DMSO) distilled on CaH, 8 g of paraformaldehyde (rendered anhydrous at ambient temperature and at a pressure of 2 torr for 8 hours), and 1.4 g of sodium ethylate dissolved in 6 mL of ethanol.
  • After having cooled the suspension by placing the flask in an ice bath (the melt temperature of the DMSO/EtOH mixture is 13°C) and while maintaining the suspension under agitation, are added threto over a period of thirty seconds, 100 mL of a solution of 16 g of fluorene in DMSO.
  • After 3 minutes from the beginning of the addition of the solution of fluorene in DMSO, the reaction is stopped by adding 1.5 mL of 37% aqueous HCl, and then the resulting mixture is diluted with 400 mL of water.
  • The mixture is saturated with NaCl, and 9,9-bis(hydroxymethyl)fluorene is extracted therefrom with ethyl acetate. The organic phase is then rendered anhydrous with anhydrous Na2SO4 and the solvent is flashed off. After toluene crystallization, 15.2 g of product (yield: 70%) is obtained.
  • The 1H-NMR spectrum of the product in CDCl3, at 200 MHz and with tetramethylsilane (TMS) as internal standard, shows the following:
    7.77 ppm, doublet, 2H aromatics
    7.62 ppm, doublet, 2H aromatics
    7.41 ppm, triplet, 2H aromatics
    7.32 ppm, triplet, 2H aromatics
    3.99 ppm, douplet, 4H CH2
    0.25 ppm, triplet, 2H OH.
    • Example 1 Synthesis of 9,9-bis(methoxymethyl)fluorene
  • Into a 100 mL flask are introduced, in nitrogen atmosphere, in order: 30 mL of tetrahydrofuran (THF), 11.3 g of 9,9-bis(hydroxymethyl)fluorene, and 31.1 mL of CH3I.
  • While agitating the flask content and operating at ambient temperature, one adds, in a period of 2 hours and 30 minutes, 4 g of NaH at 60% by weight in mineral oil, and the content is then allowed to react for 1 hour and 30 minutes.
  • The nonreacted CH3I is recorded by distillation and the remaining content is diluted with 100 mL of water; the resulting floating solid is filtered and dried under vacuum at 40°C. After ethanol crystallization, 11.3 g of product (yield: 90%) is obtained.
  • The 1H-NMR spectrum in CDCl3, at 200 MHz and with TMS as internal standard, shows the following:
    7.75 ppm, douplet, 2H aromatics
    7.65 ppm, douplet, 2H aromatics
    7.39 ppm, triplet, 2H aromatics
    7.29 ppm, triplet, 2H aromatics
    3.64 ppm, singlet, 4H CH2
    3.35 ppm, singlet, 6H CH3.
    • Comparative Example 1 Synthesis of 9,9-bis(methoxymethyl)fluorene
  • Into a 250 mL flask are introduced 36 mL of a 50% aqueous solution of NaOH, 84 mL of toluene, 9.6 g of 9,9-bis(hydroxymethyl)fluorene, and 0.24 g of tetrabutylammonium hydrogen sulfate.
  • After heating the resulting mixture to 40°C, 8 mL of CH3I are added dropwise over a period of 1 hour; at the end of the addition the content is allowed to react for 4 hours at 40°C.
  • It is then cooled to ambient temperature, diluted with 40 mL of water, and the organic phase is then separated. The aqueous phase is extracted with toluene, then the toluene extracts put together are rendered anhydrous with anhydrous Na2SO4 and the solvent is flashed off. After an ethanol crystallization 3 g of product (yield: 28%) is obtained.
    • Comparative Example 2 Synthesis of 9,9-bis(methoxymethyl)fluorene
  • Into a 250 mL flask are introduced, in anhydrous atmosphere, 100 mL of THF and 10 g of 9,9-bis(hydroxymethyl)fluorene. Then at ambient temperature 1.8 g of NaH at 60% by weight in mineral oil is added portionwise over a period of 30 minutes, and immediately thereafter 2.3 mL of CH3I are added dropwise over a period of 30 minutes. The solution is allowed to react for 3 hours.
  • A second addition is then made consisting of 1.8 g of NaH and 2.3 mL of CH3I in the same manner described above. After 3 hours of reaction time the content is diluted with 300 mL of water and then the floating solid is separated and crystallized. 5.6 g of product (yield: 50%) is obtained.
    • Polymerization Example
  • Into a 500 mL cylindrical glass reactor equipped with a filtering barrier and a stirrer are introduced at 0°C 225 mL of TiCl4, and, while under agitation over a period of 15 minutes, 10.1 g (54 mmoles) of microspheroidal MgCl2·2.1 C2H5OH obtained as described below.
  • At the end of the addition, the temperature of the reactor mixture is brought to 70°C, and 9 mmoles of 9,9-bis(hydroxymethyl)fluorene are introduced. The temperature is increased to 100°C and, after 2 hours, the TiCl4 is removed by filtration. 200 mL, of TiCl4 and 9 mmoles of 9,9-bis(hydroxymethyl)fluorene are added again; after 1 hour at 120°C the content is filtered again and another 200 mL of TiCl4 are added, continuing the treatment at 120°C for one more hour. Finally, the content is filtered and washed at 60°C with n-heptane until all chlorine ions disappear from the filtrate. The solid catalyst component obtained in this manner contains 3.5% by weight of Ti and 16.2% by weight of 9,9-bis(hydroxymethyl)fluorene.
  • The microspheroidal MgCl2·2.1 C2H5OH is prepared as follows.
  • 48 g of anhydrous MgCl2, 77 g of anhydrous C2H5OH, and 830 mL of kerosene are fed, in inert gas current and at ambient temperature, into a 2 liter reactor equipped with a turbine agitator and a drawing pipe. The content is heated to 120°C while stirring thus forming the MgCl2 alcohol adduct that melts and remains mixed with the dispersing agent. The nitrogen pressure inside the reactor is maintained at 15 atm. The drawing pipe of the reactor is heated and has an inside diameter of 1 mm, and is 3 meters long from one end of the heating jacket to the other.
  • Then the mixture is caused to flow through the pipe at a velocity of 7 m/sec ca.
  • At the exit of the pipe the dispersion is gathered in a 5 L flask, under agitation, containing 2.5 L of kerosene, and being externally cooled by way of a jacket maintained at an initial temperature of -40°C.
  • The final temperature of the emulsion is 0°C.
  • The spherical solid product that constituted the dispersed phase of the emulsion is separated by allowing it to settle and the filtrering followed by washed with heptane and drying.
  • All these operations are carried out in an inert gas atmosphere.
  • 130 g of MgCl2·3 C2H5OH in the form of spherical solid particles with a maximum diameter less than or equal to 50 micron is obtained.
  • The alcohol is removed from the product thus obtained at temperatures that are gradually increased from 50°C to 100°C in nitrogen atmosphere until the alcohol content is reduced to 2.1 moles per mole of MgCl2.
  • In a 4 liter reactor, previously purged with gaseous propylene at 70°C for 1 hour, are introduced at ambient temperature and in propylene stream 70 mL of anhydrous n-hexane containing 7 mmoles of aluminum triethyl and 4 mg of the solid catalyst component prepared as described above. The reactor is closed, 1.7 NL of hydrogen and 1.2 kg of liquid propylene are introduced; the agitator is put in motion and the temperature of the reactor mixture is increased to 70°C over a period of 5 minutes. After 2 hours at 70°C, the agitation is stopped, the nonpolymerized propylene monomer is removed, and the content is cooled to ambient temperature.
  • 380 g of polypropylene is discharged from the reactor, said polypropylene having a fraction insoluble in xylene at 25°C equal to 97.7%, and a melt index, measured according to ASTM-D 1238, condition L, of 4,5 g/10 min. The polymer yield is 95,000 g of polypropylene/g of solid catalyst component.

Claims (11)

  1. A diether having general formula (I)
    Figure imgb0007
     where A, B, C, and D are carbon atoms or heteroatoms selected from the group consisting of N, O, Si and S; v, x, and y are 0 or 1; u and z are either 0, 1, or 2;
    provided that when u = 0:
    i) A, B, and C are carbon atoms and v, x, and y are equal to 1; or
    ii) A is a nitrogen atom, B and C are carbon atoms, v is equal to 0, and x and y are equal to 1; or
    iii) A and B are nitrogen atoms, C is a carbon atom, v and x are equal to 0, and y is equal to 1; or
    iv) A and B are carbon atoms, C is a nitrogen atom, v and x are equal to 1, and y is equal to 0;
    when u = 1:
    1) A, B, C, and D are carbon atoms, v, x, and y are equal to 1, and z is equal to 2; or
    2) A and B are carbon atoms, C is a nitrogen atom, D is an oxygen atom, v and x are equal to 1, y and z are equal to 0; or
    3) A, B, and C are carbon atoms, D is an oxygen, nitrogen, sulfur, or silicon atom, v, x, and y are equal to 1, and z is equal to 0 when D is an oxygen or sulfur atom, equal to 1 when D is a nitrogen atom, and equal to 2 when D is a silicon atom;
    when u = 2:
    A, B, and C are carbon atoms, D represents two carbon atoms bonded to each other by a single or double bond, v, x, and y are equal to 1, and z is 1 when the pair of carbon atoms D is bonded by a double bond, and z is 2 when said pair is bonded by a single bond;
    radicals R and RI, equal or different, are hydrogen; halogens; C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 aralkyl radicals; the RII radicals, equal or different, are C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl; C7-C20 alkylaryl and C7-C20 aralkyl radicals, and two or more of the R radicals can be bonded to each other to form condensed cyclic structures, saturated or unsaturated, optionally substituted with RIII radicals wherein RIII is a halogen; C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 aralkyl radicals; said radicals from R to RIII optionally containing one or more heteroatoms as substitutes for carbon or hydrogen atoms, or both.
  2. The diether of formula (I) where the heteroatoms optionally present in the radicals from R to RIII are selected from the group consisting of N, S, O, P, Si, Cl, or F.
  3. The diether of claim 1 comprised in formula (II)
    Figure imgb0008
     where the radicals from R to RII are as defined for formula (I).
  4. The diether of claim 3, where the two or more R radicals are bonded to each other to form one or more condensed cyclic structures, optionally substituted by RIII radicals.
  5. The diether of claim 3, where the condensed cyclic structures are benzenic structures, optionally substituted by RIII radicals.
  6. The diether of claim 4 selected from the group consisting of:
    1,1-bis(methoxymethyl)-cyclopentadiene;
    1,1-bis(methoxymethyl)-2,3,4,5-tetramethylcyclopentadiene;
    1,1-bis(methoxymethyl)-2,3,4,5-tetraphenylcyclopentadiene;
    1,1-bis(methoxymethyl)indene;
    1,1-bis(methoxymethyl)-2,3-dimethylindene;
    1,1-bis(methoxymethyl)-4,7-dimethylindene;
    1,1-bis(methoxymethyl)-4-phenyl-2-methylindene;
    1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)indene;
    1,1-bis(methoxymethyl)-7-trimethylsilylindene;
    1,1-bis(methoxymethyl)-7-trifluoromethylindene;
    1,1-bis(methoxymethyl)-7-methylindene;
    1,1-bis(methoxymethyl)-7-cyclopenthylindene;
    1,1-bis(methoxymethyl)-7-isopropylindene;
    1,1-bis(methoxymethyl)-7-cyclohexylindene;
    1,1-bis(methoxymethyl)-7-tert-butylindene;
    1,1-bis(methoxymethyl)-7-tertbutyl-2-methylindene;
    1,1-bis(methoxymethyl)-7-phenylindene;
    1,1-bis(methoxymethyl)-2-phenylindene;
    9,9-bis(methoxymethyl)fluorene;
    9,9-bis(methoxymethyl)-2,3,6,7-tetramethylfluorene;
    9,9-bis(methoxymethyl)-2,3,4,5,6,7-hexafluorofluorene;
    9,9-bis(methoxymethyl)-2,3-benzofluorene;
    9,9-bis(methoxymethyl)-2,3,6,7-dibenzofluorene;
    9,9-bis(methoxymethyl)-2,7-diisopropylfluorene;
    9,9-bis(methoxymethyl)-1,8-dichlorofluorene;
    9,9-bis(methoxymethyl)-2,7-dicyclopentylfluorene;
    9,9-bis(methoxymethyl)-1,8-difluorofluorene;
    9,9-bis(methoxymethyl)-1,2,3,4-tetrahydrofluorene;
    9,9-bis(methoxymethyl)-1,2,3,4,5,6,7,8-octahydrofluorene;
    9,9-bis(methoxymethyl)-4-tert-butylfluorene.
    1,1-bis(α-methoxybenzyl)indene;
    1,1-bis(1'-methoxyethyl)-5,6-dichloroindene;
    9,9-bis(α-methoxybenzyl)fluorene;
    9,9-bis(1'-methoxyethyl)fluorene;
    9-methoxymethyl-9-(1'-methoxyethyl)-2,3,6,7-tetrafluorofluorene;
    9-methoxymethyl-9-pentoxymethylfluorene;
    9-methoxymethyl-9-ethoxymethylfluorene;
    9-methoxymethyl-9-(1'methoxyethyl)-fluorene; and
    9-methoxymethyl-9-[2-(2-methoxypropyl)]-fluorene.
  7. The diether of claim 1 selected from the group consisting of:
    1,1-bis(methoxymethyl)benzonaphthene;
    9,9-bis(methoxymethyl)-9,10-dihydroanthracene;
    9,9-bis(methoxymethyl)xanthene; and
    9,9-bis(methoxymethyl)-2,3,6,7-tetramethylxanthene.
  8. A process for the synthesis of a diether of general formula (III)
    Figure imgb0009
     where the R7 and R8 radicals, equal or different, are hydrogen or C1-C20 alkyl radicals, linear or branched; C3-C20 cycloalkyl, C6-C20 aryl, C7-C20 alkylaryl and C7-C20 aralkyl radicals; the R4, R5, R9, and R10 radicals, equal or different, have the same meaning as the radicals R7 and R8 radicals; the R6 and R11 radicals have the same meaning as defined for the R7 and R8 radicals except for the hydrogen; two or more radicals from R4 to R10 can be bonded to form a cyclic structure; said radicals from R4 to R11 optionally containing one or more heteroatoms, as substitutes for one or more carbon or hydrogen atoms, or both, selected from N, O, S, P, Si and halogens;
    said process comprising the following steps:
    a) mixing a diol of general formula (IV)
    Figure imgb0010
     where the radicals from R4 to R10 are as defined for general formula (III), with a compound or a mixture of compounds selected from the compounds of general formulae R6X (V), or general formula R11X (VI), where X is Cl, Br, I, CH3SO3, C6H5-SO3, or p-CH3-C6H4-SO3, or of general formula (R6)2SOn (VII), or of general formula (R11)2SOn (VIII), where R6 and R11 have the meaning as defined for general formula (III), and n is 3 or 4, in a solvent which is basically nonreactive toward the reagents; and then
    b) adding a base which is substantially inert towards the compounds of general formula (V) to (VIII), and is capable of forming the alcoholated derivative of the corresponding diol (IV) under the reaction conditions.
  9. The process of claim 8 for the synthesis of diethers of general formula (I).
  10. The process of claim 8 where the base is sodium hydride or sodium hydroxide.
  11. The process of claim 8, where the solvent is selected from the group consisting of tetrahydrofuran, dimethyl sulfoxide, diethyl ether, aliphatic or aromatic hydrocarbons, and dimethylformamide.
EP96102586A 1995-02-21 1996-02-21 Diethers suitable for use in the preparation of Ziegler-Natta catalysts Withdrawn EP0728724A1 (en)

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